Preface ......................................................... v
General Information .......................................... viii
Ligand Nomenclature ............................................. x
1 Organometallic Compounds of Main Group Elements ............ 1
1.1 General and Bonding Considerations ......................... 2
Box 1.1 Lithium ion intercalation ........................ 7
Key points ................................................. 7
Exercises .................................................. 7
1.2 Alkali Metal Organometallics: Lithium ...................... 8
1.2.1 Synthesis ........................................... 8
1.2.2 StructureofLithiumAlkyls ........................... 10
1.2.3 Reactivity of Lithium Alkyls ....................... 11
1.2.4 Organometallic Compounds of the Heavier Alkali
Metals: Na-Cs ...................................... 15
Box 1.2.4 Mixed-metal complexes and superbases ......... 17
Key points ................................................ 16
Exercises ................................................. 16
1.3 Organometallic Compounds of Alkaline Earth Metals ......... 18
1.3.1 Beryllium .......................................... 18
1.3.2 Magnesium .......................................... 18
1.3.2.1 Synthesis ...................................... 18
1.3.2.2 Structures of Magnesium Reagents ............... 23
1.3.2.3 Reactions of Magnesium Reagents ................ 24
Box 1.3.2 Grignard reagents ............................ 19
1.3.3 Calcium, Strontium, and Barium ..................... 25
Box1.3.3 Unusual Ca(1) compound ........................ 27
Key points ................................................ 27
Exercises ................................................. 27
1.4 Zinc, Cadmium, and Mercury ................................ 28
1.4.1 Zinc Compounds ..................................... 28
Box 1.4.1. Zinc alkyl purification ...................... 29
1.4.2 Cadmium Compounds .................................. 32
1.4.3 Mercury Compounds .................................. 33
1.4.3.1 Synthesis ...................................... 33
1.4.3.2 Structural Aspects ............................. 35
Box 1.4.3 Organomercury compounds in vivo ............... 36
Key points ................................................ 37
Exercises ................................................. 37
1.5 Organometallic Compounds of the Boron Group ............... 38
1.5.1 Boron Compounds .................................... 38
1.5.1.1 Synthetic Methods .............................. 43
1.5.1.2 Reactivityof Boron Compounds ................... 44
1.5.1.3 Structure and Bonding .......................... 44
Box 1.5.1.1 The importance of steric factors:
stabilization of a transition state ........ 42
Box 1.5.1.2 Boron in uncommon bonding situations ....... 45
Box 1.5.1.3 Determination of Lewis acidity ............. 45
Box 1.5.1.4 Substituent effects in boranes: C6F5
versus C6H5 ................................ 46
1.5.2 Aluminium .......................................... 46
1.5.2.1 Synthesis ...................................... 46
1.5.2.2 Structures and Properties ...................... 48
Box 1.5.2.1 27Al NMR spectroscopy ....................... 49
Box 1.5.2.2 Low-coordinate organoaluminium cations ..... 50
1.5.2.3 Reactivity ..................................... 51
Box 1.5.2.3 The structure and function of MAO .......... 53
1.5.2.4 Aluminium Compounds in Low Oxidation States .... 54
1.5.3 Gallium, Indium, and Thallium ...................... 55
1.5.3.1 Compounds in the Oxidation State III ........... 56
1.5.3.2 Ga, In, Tl Compounds in Low Oxidation States ... 58
Box 1.5.3.1 Low-valent metal alkyls and aryls ........... 60
Box 1.5.3.2 Metal alkyls as semiconductor precursors .... 62
Key points ................................................ 63
Exercises ................................................. 63
1.6 Organometallic Compounds of the Carbon Group .............. 64
1.6.1 Silicon Compounds .................................. 64
1.6.1.1 Synthetic Methods .............................. 64
1.6.1.2 Reactivity ..................................... 65
Box 1.6.1.2 Silicone polymers .......................... 66
1.6.1.3 Compounds of Low-ValentSi ...................... 68
Box 1.6.1.3 29Si NMR Spectroscopy ...................... 71
1.6.2 Germanium .......................................... 71
1.6.3 Tin Compounds ...................................... 71
Box 1.6.3 Toxicity of tin(IV) reagents ................. 72
1.6.3.1 Synthesis of Tin Compounds ..................... 72
1.6.3.2 Structures of Sn(IV) Compounds ................. 73
1.6.3.3 Reactivity of Tin Compounds .................... 74
1.6.3.4 Tin in Oxidation States +111 and +11:
Sn-Sn Bonds, Tin Radicals, and Stannylenes ..... 77
Box 1.6.3.1 Tin(II) and lone electron pairs ............ 78
Box 1.6.3.2 119Sn NMR spectroscopy ..................... 78
1.6.4 Lead Compounds ..................................... 79
Key points ................................................ 80
Exercises ................................................. 80
2 Organometallic Compounds of Transition Metals ............. 81
Box 2.0 Electron configuration and d-electron count .... 82
2.1 Ligand Types .............................................. 84
2.2 Common Types of Organometallic Complexes .................. 86
2.3 Electron Counting and the 16/18-Electron Rule ............. 91
2.3.1 Counting Conventions ............................... 91
2.3.2 Electron Counting and Oxidation States ............. 92
Key points ................................................ 95
Exercises ................................................. 95
2.4 Ligand Properties and Metal-Ligand Bonding ................ 96
2.4.1 Carbon Monoxide .................................... 96
Box 2.4.1 CO reactivity ................................ 99
2.4.2 Alkene and Alkyne Ligands .......................... 98
Box 2.4.2 13C NMR spectroscopy ........................ 101
2.4.3 n-Donor Ligands ................................... 101
2.4.4 Phosphines, Carbenes: Electronic and Steric
Parameters ........................................ 102
2.4.5 Common Co-Ligands ................................. 107
Key points ............................................... 109
Exercises ................................................ 109
2.5 L-Type n-Acceptor Ligands: Metal Carbonyl Complexes ...... 110
2.5.1 Synthesis of Metal Carbonyls ...................... 110
Box 2.5.1 Metal carbonyl complexes in biology
and medicine .................................. 112
2.5.2 Bondingin Binuclearand Cluster Complexes .......... 113
Key points ............................................... 118
Exercises ................................................ 118
2.5.3 Reaction Mechanisms of Metal Carbonyls ............ 118
2.5.3.1 Ligand Substitution: Principles and
Mechanisms .................................... 118
2.5.3.2 CO Ligand Substitution: Overview and Methods .. 122
2.5.3.3 Nucleophilic Attack on CO ..................... 124
Box 2.5.3 Nucleophilic attack on CO for hydrogen
production .................................. 125
2.5.4 Metal Carbonyl Anions ............................. 125
2.5.5 Metal Carbonyl Cations ............................ 128
2.5.6 Metal Carbonyl Halides ............................ 129
2.5.7 Metal Carbonyl Hydrides ........................... 130
2.5.7.1 Syntheses ..................................... 130
2.5.7.2 Reactions ..................................... 132
Box 2.5.7 CO reduction: the Fischer-Tropsch process ... 134
2.5.8 Related n-Acceptor Ligands ........................ 134
2.5.8.1 CS, CSe, and CTe .............................. 134
2.5.8.2 Isocyanide Complexes .......................... 135
2.5.8.3 Nitrosyl Complexes ............................ 136
Key points ............................................... 137
Exercises ................................................ 137
2.6 L-Type n-Acceptor Ligands: Alkenes, Dienes, and Alkynes .. 139
2.6.1 Alkene Complexes .................................. 141
2.6.1.1 Synthesis of Alkene Complexes ................. 141
2.6.1.2 Reactions of Alkene Complexes ................. 145
2.6.2 Diene Complexes ................................... 150
2.6.2.1 Synthesis of Conjugated Diene Complexes ....... 150
2.6.2.2 Bonding in Complexes of Conjugated Dienes ..... 151
Box 2.6.2.2 Molecular wires and switches .............. 154
2.6.2.3 Reactions of Conjugated Diene Complexes ....... 153
Box 2.6.2.3 Nucleophilic attack on n-ligands:
the Davies-Green-Mingos rules ............. 157
2.6.3 Alkyne Complexes .................................. 158
2.6.3.1 Synthesis of Alkyne Complexes ................. 160
2.6.3.2 Reactivity of Alkyne Complexes ................ 161
Box 2.6.3 Alkyne complexes in organic synthetic
methodology ................................. 165
Key points ............................................... 168
Exercises ................................................ 168
2.7 LX- and L2X-Typen-Ligands: Allyl and Enyl Complexes ...... 169
2.7.1 Metal Allyl Complexes ............................. 169
2.7.1.1 Synthesis ..................................... 169
2.7.1.2 Properties .................................... 171
2.7.1.3 Reactivity of Allyl Complexes ................. 172
Box 2.7.1.3 Metal allyl catalysts ..................... 175
2.7.2 Metal Dienyl and Trienyl Complexes ................ 177
2.7.2.1 Synthesis ..................................... 177
2.7.2.2 Reactivity .................................... 178
Box 2.7.2.2 Metal dienyl complexes in organic
synthesis ................................. 178
Key points ............................................... 179
Exercises ................................................ 179
2.8 L2X-Type n-Acceptor Ligands: Metallocene Complexes ....... 180
2.8.1 Bis(cyclopentadienyl) Complexes ................... 180
2.8.1.1 Synthesis of Metallocene Complexes ............ 185
2.8.1.2 Structure and Bonding in MCp2 Complexes ....... 185
2.8.1.3 Reactions of MCp2 Complexes ................... 188
Box 2.8.1.3 Ferrocenes in medicine and catalysis ...... 191
2.8.2 Bent Metallocene Complexes ........................ 194
2.8.2.1 Synthesis of Bent Sandwich Complexes .......... 194
2.8.2.2 Structures of Bent Metallocene Complexes ...... 196
2.8.2.3 Reactivity of Bent Metallocene Complexes ...... 198
Box 2.8.2.1 Structural aspect of electrophilic
metallocenes: square-planarand trigonal-
bipyramidal С ............................. 201
Box 2.8.2.2 Metallocene materials: single-molecule
magnets (SMMs) ............................ 203
Key points ............................................... 204
Exercises ................................................ 204
2.8.3 Mono-Cyclopentadienyl (Half-Sandwich) Complexes ... 204
2.8.3.1 Synthesis of Mono-Cp Complexes ................ 205
2.8.3.2 Reactivity of Mono-Cp Complexes ............... 207
Box 2.8.3 Half-sandwich complexes in stereoselective
synthesis ................................... 209
Key points ............................................... 211
Exercises ................................................ 211
2.9 Arene Complexes .......................................... 212
2.9.1 Bis(Arene) Sandwich Complexes ..................... 212
2.9.1.1 Synthesis and Structures ...................... 212
2.9.1.2 Reactivity of Bis(Arene) Complexes ............ 214
2.9.2 Arene Half-Sandwich Complexes ..................... 215
2.9.2.1 Synthesis and Structures of Mono-Arene
Complexes ..................................... 216
Box2.9.2.1 Mono-arenecomplexesforcancertreatment ...... 217
2.9.2.2 Reactivity of Mono-Arene Carbonyl Complexes ... 218
2.9.3 Arene Complexes with Less Common Coordination
Modes ............................................. 221
2.9.4 Larger Arene Ligands: 7-, 8- and 9-Membered
Rings ............................................. 222
2.9.4.1 n-C7H7 Complexes .............................. 222
2.9.4.2 n-C8H8 Complexes .............................. 223
2.9.4.3 n-C9H9 Complexes .............................. 225
2.9.4.4 n-Complexes of Heterocycles ................... 225
Key points ............................................... 227
Exercises ................................................ 227
2.10 Sigma Complexes .......................................... 228
2.10.1 H2 Complexes ...................................... 228
2.10.2 Alkane and Silane complexes ....................... 229
Box 2.10.2 Alkane dehydrogenation and
functionalization ........................... 232
Key points ............................................... 234
2.11 Complexes with M-Co-Bonds ................................ 235
2.11.1 Energeticsand Reactivity of Metal Alkyls .......... 235
2.11.2 Types and Bonding Modes of M-C σ-Bonded Ligands ... 237
2.11.2.1 M-R Ligand Types .............................. 237
2.11.2.2 M-R Bonding Modes ............................. 238
2.11.2.3 The Importance of Steric Hindrance ............ 240
2.11.3 Synthesis of Metal Alkyls ......................... 242
2.11.3.1 Synthesis of Homoleptic Metal Alkyl
Complexes ..................................... 242
Box 2.11.3.1 The structures of homoleptic metal methyl
complexes ................................... 245
2.11.3.2 Synthesis of Heteroleptic Metal Alkyl
Complexes ..................................... 245
Box 2.11.3.2 Synthetic examples ........................ 252
2.11.3.3 Alkynyl Complexes ............................. 256
2.11.4 Reactivity of Metal Alkyls ........................ 257
2.11.4.1 M-C Bond Protonolysis ......................... 258
2.11.4.2 Cleavage by Halogens .......................... 259
2.11.4.3 Chalcogen Insertions .......................... 259
2.11.4.4 Cleavage by Lewis Acids ....................... 260
2.11.4.5 Cleavage by Oxidation ......................... 260
2.11.4.6 Hydrogenolysis of M-C Bonds ................... 261
2.11.4.7 Insertion of Electrophilic Heterocumulenes .... 261
Box 2.11.4.7 CO2 utilization in synthesis .............. 262
2.11.4.8 Insertion of NO ............................... 263
2.11.4.9 Insertion of CO ............................... 263
2.11.4.10 Insertion of Isocyanides ..................... 267
2.11.4.11 Insertion of Alkenes ......................... 268
2.11.4.12 Insertion of Alkynes ......................... 270
2.11.4.13 Reactions of Metal Alkyls with Non-Innocent
Ligands ...................................... 271
Box 2.11.4.12 Transition metal alkyl complexes
in vivo .................................. 272
Key points ............................................... 274
Exercises ................................................ 274
2.12 Alkylidene Complexes ..................................... 275
Box 2.12 NMR spectroscopy of metal carbenes ........... 276
2.12.1 Synthesis of Alkylidene Complexes ................. 276
2.12.1.1 Synthesis of Alkylidene Complexes in Low
Oxidation States: Fischer Carbenes ............ 276
2.12.1.2 Synthesis of Alkylidene Complexes in High
Oxidation States (d0) ......................... 279
2.12.1.3 Vinylidene Complexes .......................... 281
Box 2.12.1.2 Alkynyl-allenylidene rearrangements ....... 282
2.12.2 Reactivity of Alkylidene Complexes ................ 282
2.12.2.1 Reactions of Fischer Carbenes ................. 282
Box 2.12.2.1 The Dötz reaction ......................... 284
2.12.2.2 Reactions of d0 Alkylidene Complexes .......... 283
2.12.2.3 Ruthenium Carbene Complexes ................... 288
Box 2.12.2.3 Applications of Olefin Metathesis ......... 289
Key points ............................................... 292
Exercises ................................................ 292
2.13 Complexes with M ≡ C Triple Bonds: Carbynes .............. 293
2.13.1 Synthesis of Carbyne Complexes .................... 293
2.13.2 Reactions of Carbyne Complexes .................... 295
2.13.3 Bridging Carbene and Carbyne Complexes ............ 296
Key points ............................................... 297
Exercises ................................................ 297
3 Homogeneous Catalysis with Organometallic Transition
Metal Complexes .......................................... 299
3.1 General Considerations ................................... 301
3.2 Key Reaction Steps in Homogeneous Catalysis .............. 304
3.2.1 Catalyst Activation ............................... 304
3.2.2 Oxidative Addition ................................ 305
3.2.3 Reductive Elimination ............................. 307
3.2.4 Nucleophilic Attack on Coordinated Substrates ..... 309
Key points ............................................... 309
Exercises ................................................ 310
3.3 Catalytic H-H and H-X Additions .......................... 311
3.3.1 Hydrogenation ..................................... 311
3.3.1.1 General hydrogenation Catalysis ............... 311
3.3.1.2 Arene Hydrogenation ........................... 314
3.3.1.3 Asymmetric Hydrogenation ...................... 315
Box 3.3.1.3 Applications of asymmetric
hydrogenations ............................ 319
3.3.1.4 Transfer hydrogenation ........................ 321
Box 3.3.1.4 Hydrogen storage molecules and H2
release ................................... 322
3.3.1.5 Outer-Sphere hydrogenation of Ketones ......... 322
3.3.2 Hydrosilylation ................................... 323
3.3.3 Isomerizations .................................... 324
3.3.4 Hydrocyanation .................................... 325
Box 3.3.4 Applications of asymmetric hydrocyanation ... 328
3.3.5 Hydroamination .................................... 329
Key points ............................................... 330
Exercises ................................................ 331
3.4 Catalytic Carbonylations ................................. 332
3.4.1 Hydroformylation .................................. 332
3.4.2 Carbonylation Reactions ........................... 334
3.4.2.1 Alcohol Carbonylations ........................ 334
3.4.2.2 Alkene and Alkyne Carbonylations .............. 336
Key points ............................................... 339
Exercises ................................................ 340
3.5 Alkene Oxidations ........................................ 341
Key points ............................................... 342
3.6 Coupling Reactions ....................................... 343
3.6.1 C-C Cross-Coupling Reactions ...................... 344
3.6.2 C-N Cross-Coupling Reactions ...................... 345
3.6.3 Coupling Reactions with Carbonylation ............. 345
3.6.4 HeckArylations .................................... 346
Box 3.6.4 Mechanistic aspects of the Heck reaction ... 346
Key points ............................................... 347
Exercises ................................................ 347
3.7 Alkene Polymerizations ................................... 349
3.7.1 Ziegler Catalysts ................................. 349
3.7.1.1 Catalyst Composition .......................... 349
Box 3.7.1.1 Polymersand polymer structure ............. 350
3.7.1.2 Mechanism of Ziegler Catalysts ................ 353
3.7.2 Metal Complexes as Polymerization Catalysts ....... 355
3.7.2.1 Catalyst Activation and Active Species ........ 356
3.7.2.2 Alkene Polymerization Reactions ............... 359
3.7.2.3 Stereoselective Polymerization ................ 362
Box 3.7.2.3 Chain-shuttling polymerization ............ 365
3.7.3 Alkene Oligomerizations ........................... 366
Key points ............................................. 368
Exercises .............................................. 368
Appendix 1 Commonly Used Solvents and Their Properties ....... 369
Appendix 2 Number and Symmetry of Infrared-Active
Vibrations of Metal Carbonyl Complexes ............ 373
Appendix 3 Answers to Exercises .............................. 374
Appendix 4 Further Reading ................................... 393
Index ......................................................... 405
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